Polymer compositions

ABSTRACT

Polymer compositions which are useful to improve water repellency and durability in fiber, nonwoven, textile, and paper compositions are disclosed. A method of improving water repellency and durability in fiber, nonwoven, textile, and paper compositions is also disclosed.

This is a divisional of application Ser. No. 09/099,312 filed Jun. 18,1998, allowed, which claims benefit of provisional application60/050,390 filed Jun. 20, 1997.

This invention relates to polymer compositions, more specifically thisinvention relates to polymer compositions which are useful as binders infiber, nonwoven, textile, and paper compositions.

Fiber, nonwoven, textile, and paper compositions typically are coatedwith polymeric binders to provide water repellency and durability. Selfcross-linking acrylic polymers and styrene/acrylic polymers aretypically used in these applications. There is a need for polymericbinders which provide improved water repellency and durability in fiber,nonwoven, textile, and paper compositions.

U.S. Pat. No. 5,521,266 discloses a method for forming polymers fromhydrophobic monomers. The disclosed method utilizes macromolecularorganic compounds which have a hydrophobic cavity to complex monomerswhich have low water solubility. This enables the formation of polymersfrom low water solubility monomers by emulsion polymerization. Suitablemonomers for use in the method for forming polymers include laurylmethacrylate.

U.S. Pat. No. 3,915,921 discloses interpolymers made by solutionpolymerization. The interpolymers contain hydrophobic monomers includingstearyl methacrylate, and certain carboxylic monomers including acrylicacid. The interpolymers are taught to be effective thickeners.

Despite the disclosure of the prior art, there is a continuing need forpolymeric binders which provide improved water repellency and durabilityin fiber, nonwoven, textile, and paper compositions.

We have surprisingly found that the use of the polymer compositions ofthis invention provide improved water repellency and durability infiber, nonwoven, textile, and paper compositions.

The present invention provides a composition comprising an emulsionpolymer comprising as polymerized units:

i) a) from 9.5 to 99.9 parts by weight of at least one C₁₂ to C₄₀ alkylester of (meth)acrylic acid;

b) from 0 to 90 parts by weight of at least one less than C₁₅ethylenically unsaturated nonionic monomer;

c) from 0 to 90 parts by weight of at least one ethylenicallyunsaturated acid containing monomer or salts thereof; and

d) from 0.1 to 10 parts by weight of at least one cross-linking monomer;and

ii) from 0 to 10 parts by weight, based on the polymer weight of atleast one cross-linking agent,

provided that the composition contains 0.1 to 10 parts by weight, basedon the polymer weight cross-linking monomer and cross linking agent.

In another embodiment, the present invention provides a method ofimproving water repellency and durability in fiber, nonwoven, textile,and paper compositions comprising:

a) providing a composition comprising an emulsion polymer comprising aspolymerized units:

i) from 9.5 to 100 parts by weight of at least one C₁₂ to C₄₀ alkylester of (meth)acrylic acid;

from 0 to 90 parts by weight of at least one less than C₁₅ ethylenicallyunsaturated nonionic monomer;

from 0 to 90 parts by weight of at least one ethylenically unsaturatedacid containing monomer or salts thereof; and

from 0 to 10 parts by weight of at least one cross-linking monomer; and

ii) from 0 to 10 parts by weight, based on the polymer weight of atleast one cross-linking agent;

b) providing a substrate selected from the group consisting of fiber,nonwoven, textile, and paper;

c) coating the substrate with the polymer composition; and

d) drying the coated substrate.

The present invention also provides an article comprising:

a substrate selected from the group consisting of fiber, nonwoven,textile, and paper coated with an emulsion polymer compositioncomprising as polymerized units:

i) from 9.5 to 100 parts by weight of at least one C₁₂ to C₄₀ alkylester of (meth)acrylic acid;

from 0 to 90 parts by weight of at least one less than C₁₅ ethylenicallyunsaturated nonionic monomer;

from 0 to 90 parts by weight of at least one ethylenically unsaturatedacid containing monomer or salts thereof; and

from 0 to 10 parts by weight of at least one cross-linking monomer; and

ii) from 0 to 10 parts by weight, based on the polymer weight of atleast one cross-linking agent.

The compositions of this invention may be prepared by a single stage ormulti-stage process. The process may be an emulsion polymerization suchas the process described in U.S. Pat. No. 5,521,266. The process mayalso be solution polymerization followed by emulsification as describedin U.S. Pat. No. 5,539,021, mini-emulsion polymerization, ormicro-emulsion polymerization. Emulsion polymerization is preferred. Inthe process utilized for preparing the samples within this application,a first stage was prepared by adding a monomer emulsion and sodiumpersulfate to a solution containing methyl-β-cyclodextrin (“CD”),deionized water, and surfactant. The first stage was reacted at 85° C. Asecond stage was prepared by making a second monomer emulsion andfeeding the second monomer emulsion and a sodium persulfate solution tothe reacted first stage. The second stage was reacted at 85° C.

The compositions of this invention contain as polymerized units from 9.5to 100 parts by weight, preferably from 15 to 80 parts by weight, morepreferably 20 to 70 parts by weight of at least one C₁₂ to C₄₀ alkylester of (meth)acrylic acid. It is preferred that the alkyl ester of(meth)acrylic acid be a C₁₂ to C₃₀ alkyl ester of (meth)acrylic acid. Itis more preferred that the alkyl ester of (meth)acrylic acid be a C₁₂ toC₁₈ alkyl ester of (meth)acrylic acid. Suitable alkyl esters of(meth)acrylic acid include cetyl (meth)acrylate, stearyl (meth)acrylate,behenyl (meth)acrylate, and eicosyl (meth)acrylate. Beneficialproperties may be obtained by utilizing more than one C₁₂ to C₄₀ alkylester of (meth)acrylic acid.

The compositions of this invention also contain as polymerized unitsfrom 0 to 90 parts by weight, preferably 15 to 90 parts by weight, morepreferably 20 to 80 parts by weight of at least one less than C₁₅ethylenically unsaturated nonionic monomer. Suitable less than C₁₅ethylenically unsaturated nonionic monomers for use in the preparationof the polymer compositions of this invention include, but are notlimited to (meth)acrylic ester monomers including methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methylmethacrylate, butyl methacrylate, hydroxyethyl methacrylate, andhydroxypropyl acrylate; acrylamide or substituted acrylamides; styreneor substituted styrene; vinyl acetate or other vinyl esters; vinylmonomers such as vinyl chloride, vinylidene chloride, N-vinylpyrolidone; and acrylonitrile or methacrylonitrile. Butyl acrylate,methyl methacrylate, and styrene are preferred. More preferred are butylacrylate and methyl methacrylate.

The compositions of this invention also contain as polymerized unitsfrom 0 to 90 parts by weight, preferably 0.1 to 50 parts by weight, morepreferably 1 to 10 parts by weight ethylenically unsaturated acidcontaining monomer or salts thereof. Suitable ethylenically unsaturatedacid containing monomers include, but are not limited to acrylic acid,methacrylic acid, crotonic acid, phosphoethyl methacrylate,2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate,itaconic acid, fumaric acid, maleic acid, monomethyl itaconate,monomethyl fumarate, monobutyl fumarate, and maleic anhydride. Acrylicacid and methacrylic acid are preferred. Methacrylic acid is morepreferred.

The compositions of this invention also contain as polymerized unitsfrom 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight,more preferably 0.1 to 3 parts by weight, based on the polymer weight ofa cross-linker selected from a cross-linking agent and a cross-linkingmonomer. By cross-linker is meant a compound which has at least 2reactive groups which will react with acid groups found on the monomersof the compositions of this invention. Cross-linking agents useful inthis invention include a polyaziridine, polyisocyanate,polycarbodiimide, polyamine, and a polyvalent metal. The cross-linkingagent is optional, and may be added after polymerization has beencompleted.

Cross-linking monomers are cross-linkers which are incorporated with themonomers of the compositions of this invention during polymerization.Cross-linking monomers useful in this invention include divinyl benzene,(meth)acryloyl polyesters of polyhydroxylated compounds, divinyl estersof polycarboxylic acids, diallyl esters of polycarboxylic acids, diallyldimethyl ammonium chloride, triallyl terephthalate, methylene bisacrylamide, diallyl maleate, diallyl fumarate, hexamethylene bismaleamide, triallyl phosphate, trivinyl trimellitate, divinyl adipate,glyceryl trimethacrylate, diallyl succinate, divinyl ether, the divinylethers of ethylene glycol or diethylene glycol diacrylate, polyethyleneglycol diacrylates or methacrylates, 1,6-hexanediol diacrylate,pentaerythritol triacrylate or tetraacrylate, neopentyl glycoldiacrylate, cyclopentadiene diacrylate, the butylene glycol diacrylatesor dimethacrylates, trimethylolpropane di- or tri-acrylates,(meth)acrylamide, n-methylol (meth)acrylamide, mixtures thereof, and thelike. (Meth)acrylamide, n-methylol (meth)acrylamide, and mixturesthereof are preferred. The amount of cross-linker utilized is chosensuch that the cross-linker does not interfere with film formation.

Chain transfer agents may be used to control the molecular weight of thepolymer composition. Suitable chain transfer agents include mercaptans,such as, for example, dodecylmercaptan. The chain transfer agent may beused at from 0.1% to 10% based on the total weight of the polymericcomposition.

The polymer compositions of this invention are useful in fiber,nonwoven, textile, and paper compositions.

The polymer compositions of this invention are typically used in fiber,nonwoven, textile, and paper compositions. A substrate such as fiber,nonwoven, textile, or paper is coated or treated with the polymercomposition by dipping the substrate in the polymer composition or byspraying the polymer composition onto the substrate. The coatedsubstrate is then dried at a temperature from ambient to 200° C. Thesubstrate may then be cured at temperatures from ambient to 200° C. Itis preferred that enough polymer composition is utilized to give abinder add-on of from 2% to 200% on finished product weight. It is morepreferred that enough polymer composition is utilized to give a binderadd-on of from 10% to 50% on finished product weight.

The following abbreviations are used throughout this patent application:LMA=lauryl methacrylate SMA=stearyl methacrylate St=styrene MMA=methylmethacrylate BA=butyl acrylate MAA=methacrylic acid nDDM=n-dodecylmercaptan Id.=sample identification number CD=methyl-β-cyclodextring=grams ° C.=degrees centigrade (meth)acrylate=methacrylate and acrylatecc=cubic centimeter MMAM=50% methacrylamide/50% n-methylolmethacrylamide cm=centimeter MAM=90% n-methylol acrylamide/10%acrylamide mm=millimeter oz/sq yd=ounce/square yard ml=milliliterpsi=pounds per square inch Abs.=absorbance RH=relative humiditywt=weight rpm=rotations per minute

The following Table lists some of the materials used in this patentapplication and their sources:

Material Function Source Triton ® XN-45S surfactant Union CarbideFC ®-280 fluorochemical 3M Company Michem Lube ® 743 wax McGee Mikon ®NRW-3 surfactant Sequa Chemical Company Aircel ® PC-6A methylatedmelamine Borden (Astro Industries) Cymel ® 303 melamine Cytek Scotch ®Magic Tape Tape 3M Company Triton ® X-100 surfactant Union Carbide

EXAMPLE 1

For stage 1, 400 g deionized water, 11.9 g Triton® XN-45S anionicsurfactant (58%), and CD (Table 1, 53% solution in water) wereintroduced into a 4-liter round bottom flask with four necks equippedwith a mechanical stirrer, temperature control device, condenser,monomer and initiator feed lines, and a nitrogen inlet at roomtemperature. The contents were heated to 85° C. while stirred under anitrogen purge. A monomer emulsion of 31.3 g deionized water, 0.4 gTriton® XN-45S anionic surfactant, 33.8 g LMA, 7.5 g BA, 33 g MMA, and0.75 g MAA was prepared separately. Solutions of 0.35% by weight sodiumcarbonate (based on the total monomer weight in stage 1 and stage 2) in25 g deionized water and 0.35% by weight sodium persulfate (based on thetotal monomer weight in stage 1 and stage 2) in 30 g deionized waterwere introduced into the reaction kettle. The monomer emulsion was fedover a period of 20 minutes together with an initiator solution of 0.05%sodium persulfate (based on the total monomer weight in stage 1 andstage 2) in 210 g deionized water.

For stage 2, a monomer emulsion was prepared using 625 g deionizedwater, 7.8 g Triton® XN-45S anionic surfactant, and monomers accordingto Table 1. Immediately after the end of the stage 1 monomer emulsionfeed, the stage 2 monomer emulsion was fed over a period of 3 hourstogether with the sodium persulfate initiator solution.

TABLE 1 Id. LMA SMA BA MMA MAA MAM MMAM CD  1 300  0 525 660 15  0  014.3  2 675  0 225 585 15  0  0 14.3  3 780  0  0 705 15  0  0 14.3  4 0 975  0 480 15  0 30 28.6  5  0 975  0 510 15  0  0 28.6  6  0 750 285450 15  0  0 28.6  7 750  0 435 270 15 30  0 14.3  8  0 975  0 480 15 30 0 28.6  9 750  0 735  0 15  0  0 14.3 10  0 975  0 510 15  0  0 28.6

Samples 4, 7, and 8 are examples of the compositions of this invention.All samples demonstrate the usefulness of the compositions in fiber,nonwoven, textile, and paper applications.

EXAMPLE 2 Application Testing—Impact Penetration Test

The impact penetration test measures the resistance of fabrics to thepenetration of water by impact. (AATCC Test Method 42-1989) Samples thatperform well in this test as indicated by water penetration of less than1 g are considered to be good candidates as coatings/treatments fornonwoven and paper compositions.

To prepare samples for the test, a pulp substrate (Whatman Filter PaperNo:4) was padded with a composition of this invention. The bath solidswere 35% and the pad pressure was approximately ¾bar. Samples weredried/cured for 3 minutes at 149° C. to give a binder add-on of 26% onfinished product weight. The sample was tested in triplicate and theresults were averaged.

The Impact Penetration test was run by pouring 500 mils of water througha spray nozzle and letting it impact a test fabric at a 45° angle andthen measuring the amount of the water that penetrated the web andcollected on a piece of blotter paper underneath the test sample. Theresults are shown in Table 2.

TABLE 2 Amount of water penetration Sample (g) 6 0.3

The above data shows that a pulp substrate bonded with an SMA-containingcomposition is useful as a coating in nonwoven and paper compositions.

EXAMPLE 3 Application Testing—Water Absorption

The water absorption test was run to evaluate the hydrophobic propertiesof the compositions of this invention by measuring the percent waterabsorption of dried/cured films. Samples which perform well in this testas indicated by a percent water absorption of less than 35% areconsidered to be useful as coatings/treatments in nonwoven, textile, andpaper compositions.

A film was prepared by drying latex in a container overnight. The filmwas then fully dried/cured for 3 minutes at 149° C. Film thicknessranged from 10-15 mils. The percent water absorption of various polymerswas determined on dried/cured film samples with dimensions of 2.54cm×2.54 cm×10 mils after allowing the films to soak in water for 48hours. Samples were run in duplicate and averaged. The percent waterabsorption was determined for the compositions of this invention byusing the following equations:${\% \quad {Water}\quad {Absorption}} = {\frac{{Wf} - {Wi}}{Wi} \times 100}$

Where

Wi=the initial weight of the film

Wf=the final weight of the film after soaking in water for 48 hours.

The results are shown in Table 3.

TABLE 3 Sample Percent Water Absorption 6 14.6 3 12.4 5  7.9

The data above indicates that the compositions are useful ascoatings/treatments in nonwoven, textile, and paper compositions.

EXAMPLE 4 Application Testing—Tensile Testing and Handle-O-Meter

This test was run to demonstrate the utility of the compositions of thisinvention as coatings/treatments for nonwovens. It is known thatpolymers with high strength as indicated by tensile strength, normallyare not acceptably soft. The acceptability of the binder is determinedby scores of greater than 1,000 g for dry tensile; greater than 600 gfor wet tensile; and greater than 300 g for isopropanol (IPA). Theacceptable score for Handle-O-Meter is 50 grams force or less.

Pad Saturation: A 1 oz/sq. yd. polyester web was saturated with binderand dried/cured at 149° C. for 3 minutes. All samples had approximately40% binder add-on based on fiber weight. From these sample webs tensileand Handle-O-Meter testing was done. The saturation formulation was asfollows (8% Bath solids):

211.6 g Binder

4.8 g Catalyst 1.5% solids on solids (25% NH₄NO₃)

783.6 g Water

Tensile Testing: A 2.54×12.7 cm web sample with long axis in the crossmachine direction was evaluated using a Intelect 500 Thwing AlbertTesting Instrument. The instrument was set to have a 10.2 cm gaugelength and a crosshead speed of 30.5 cm/minute. Dry, wet and Isopropanoltensile testing was done on an average of at least 7 sample strips. Wettensiles were obtained by soaking the web strips in 0.1% Triton® X-100surfactant for 30 minutes. Isopropanol tensiles were obtained by soakingthe web strips for 30 minutes in Isopropanol. Results were reported ingrams/2.54 cm.

Handle-O-Meter: Handle-O-Meter measurements were obtained from a10.2×10.2 cm web sample. Measurements were made using a Thwing AlbertDigital Handle-O-Meter (Model 211-5) using a 0.64 cm gap. The instrumentmeasured the resistance to bend the nonwoven through a slit of a certainwidth. Results were reported in grams force. An average reading ofmachine and crossmachine direction from at least four samples each wasobtained. The results of Tensile and Handle-O-Meter testing are shown inTable 4.

TABLE 4 Dry Wet IPA Sample Tensile Tensile Tensile Handle-O-Meter 5 20921339 546 107 90% 7/10% 8 1155  870 358  42 (blend)

The compositions have acceptable softness of hand and offer excellentdry and wet tensile strength, and therefore are useful ascoatings/treatments in nonwoven compositions.

EXAMPLE 5 Application Testing—Mason Jar Test for Water Repellency

This test was run to evaluate the water repellent/barrier properties ofthe compositions of this invention. The Mason Jar Test measured theresistance of a nonwoven fabric to the penetration of an aqueous sodiumchloride solution under a hydrostatic head. This test can be used tomeasure how well a medical nonwoven fabric repels fluids. Samples areconsidered to be acceptable when they demonstrate a score of 120 minutesor greater.

The test was run by placing a swatch of the test fabric in place of theflat metal lid, adding 510 mls of 0.9% saline solution to the jar,inverting the jar (which has a hole in the bottom to equalize thepressure) and measuring the time it takes for the water to penetrate thefabric.

The samples used for the Mason Jar test were prepared in the followingmanner: A 1 oz/sq.yd. polyester web was padded using abinder/fluorochemical/wax bath. The solids of the bath were 35% and thepadder pressure was ¾bar. A composition of this invention was evaluated.The padded samples were dried/cured for 3 minutes at 149° C. Totalbinder add-on was approximately 40% (based on finished product weight).Each sample was tested by the Mason Jar Test in triplicate and theresults were averaged. The pad formulation was as follows (35% bathsolids):

111 g Binder

8.1 g FC®-280 (5.6% Solids on binder solids)

18.75 g Michem Lube® 743 (wax) (12.0% Solids on Binder solids)

1.25 g Mikon® NRW-3 (2.5% Wet on binder solids)

30 g Water

The results are shown in Table 5.

TABLE 5 Sample Time 6 120-300 minutes

The sample demonstrated an acceptable score and, therefore is considereduseful as a coating/treatment for medical nonwoven compositions.

EXAMPLE 6 Application Testing—Water Vapor Transmission

This test was run to determine the rate for water to permeate through afilm. Samples that perform well in this test, as indicated by a WVTR of1 g/hour×meter squared are considered to be useful in nonwovenapplications.

The test method used was Water Cup Method of ASTM E96-80. In thismethod, 30 mils of distilled water was added to a plastic cup. A polymerfilm (15-20 mils thick) which was dried/cured at 149° C. for 3 minuteswas then placed over and sealed to the mouth of the cup using a threadedplastic ring. The cup was then placed in a constant temperature andhumidity room (24° C./50% relative humidity) and periodic weighings ofthe cup were made to determine the rate of water movement through thepolymer film to the controlled atmosphere. The weight loss was plottedagainst time until a nominal steady state existed. The slope of thestraight line was the water vapor transmission rate. The water vaportransmission rate (WVTR) was determined using the following equation:${WVTR} = \frac{G}{\left( {T \times A} \right)}$

Where:

G=weight change

T=time

A=test area (mouth cup area)

WVTR was expressed in units of grams/hour×meter sq.

The results are shown in Table 6.

TABLE 6 Sample WVTR 5 0.19 g/hour × meter sq

The composition provides a good moisture barrier and therefore isconsidered to be useful as a coating/treatment in nonwoven compositions.

EXAMPLE 7 Application Testing—Flock Evaluation

This test was run to determine the potential for the compositions ofthis invention to be used as binders for flocked fiber applications.

Flock formulations were a blend of 70% 9/30% 10 which were mixed with 5%Clay and 1% Ammonium Stearate. The samples were formulated toapproximately 43% solids and a Brookfield LVT viscosity of 19,000 millipascal seconds (#4 spindle at 6 rpm). Osnaburg Polyester Cotton Fabricwas the substrate for testing. The target add-on was 2.5-3.0 oz/sq yd.The sample was flocked with 3 denier flock using alternating current.The Flocked fabrics were dried and cured for 3 minutes at 150° C.Samples were evaluated with and without 2% Aircel PC-6A (melamineformaldehyde cross-linker). The Flocked fabrics were evaluated for: washdurability—cuff edge abrasion after five hot wash cycles, acceptablescores are between 4 and 5; and the British two pense scuff testevaluating abrasion, acceptable retention of scuff wet versus dry isgreater than 30%. The scuff test was modified for flocked fabrics,counting the number of scuffs it took until adhesive failure was noted.The tests were run dry and wet. The results are shown in Tables 7, and8.

TABLE 7 Flocked Fabric Evaluation (Wash Test) Sample Result Rating 70%9/30% 10 Complete flock removal 1 70% 9/30% 10 with Cymel 303 >90% flockretention 4

TABLE 8 Retained Wet Abrasion (British Two Pense Test) Sample Result 70%9/30% 10 59% 70% 9/30% 10/Aircel ® PC-6A 91%

The above results indicate that the compositions are useful as bindersfor fiber applications.

EXAMPLE 8 Applications Testing—Decorative Laminates

These tests were performed to demonstrate the utility of thecompositions of this invention as binders in decorative laminateapplications.

Saturant Composition

Latex/urea formaldehyde resin mixtures were prepared at 38% total latexand urea formaldehyde resin solids. Fifty parts of latex solids werecombined with 50 parts of urea formaldehyde resin solids.

Saturation of sheets

A paper sheet was saturated using the above mixture by first floatingthe pre-weighed sheet on the mixture surface for 20 seconds, followed byimmersion for 10 seconds. The penetration time was recorded as theelapsed time (in seconds) required for the saturant to completely strikethrough from the bottom side to the top surface of the sheet.Immediately after completing the saturation, the sheet was passedthrough a padder using a single pass at 12 psi to remove excesssaturant. The wet sheet was weighed and the % pick up was calculated.The saturated sheet was cured for 2 minutes at 150° C. Acceptable scoresfor % pick-up are 20% to 60%.

Water Absorptiveness (Cobb Test)

A modified procedure of TAPPI Test Method T 441 om-84 was used toconduct this test. The method measured the quantity of water absorbed bythe paper in a specified time under standardized conditions. A 12.7 cmby 12.7 cm square sample was tested. The procedure was modified to use25 ml water instead of the 100 ml specified in the method, reducing thehead from 1.0 cm to 0.25 cm. The test period was shortened from 120seconds to 60 seconds. One ply of paper was tested at a time. Theabsorptiveness was calculated as the weight of water absorbed in gramsper square meter. Acceptable scores are less than 20 grams per squaremeter.

Flexibility

Flexibility of the paper was determined by pre-conditioning three 1.5 cmby 4 cm specimens at 50% relative humidity and 21° C. for 24 hours andrapidly bending the specimens over a mandrel. A single test stripafforded testing of at least 3 different mandrel sizes. The mandreldiameter, measured to mm, which did not cause cracking of the samplesurface was recorded as the pass point. The average of the 3 passingvalues was reported as the flexibility at 50% relative humidity. Smallermandrel diameter correlated with increasing flexibility. Flexibility atlow relative humidity was measured by drying 3-1.5 cm by 4 cm specimensfor 5 minutes at 85° C. in a forced air oven, followed by rapidlybending the sample strip over the mandrel. The average mandrel diameterwhich did not cause cracking of the paper under these conditions wasreported as the flexibility at low humidity. Acceptable scores for 50%RH and low % RH are less than 30 millimeters.

Scotch Tape Delamination Resistance

This test measured the cohesive strength of a single ply of paper todelamination of the ply when a 2.54 cm by 2.54 cm surface of the paperwas contacted with Scotch Magic Tape™ for 5 seconds and for 24 hours atconditions of 50% relative humidity and 21° C. At each time interval,the tape was rapidly pulled by hand from the paper in the oppositedirection from which the tape was applied. The percentage of the tapesurface within the 2.54 cm contact area which showed no evidence offiber removal was recorded as the delamination resistance of the sampleimmediately (5 seconds) after application of the tape or after 24 hoursof contact. Acceptable scores are greater than 50%. The results of thesetests are shown in Tables 9 and 10.

TABLE 9 Sample Penetration Speed Wt % Dry Pick-Up 1 1 46 2 1 46.2

TABLE 10 Tape Delamination Mandrel Cobb Resistance Flexibility (mm)Sample Water Abs. Initial 24 Hours 50% RH Low % RH 1 8.5 100 73 1.75 2.82 6.5  97 78 1.5  3.1

The data above indicate that the compositions are useful in decorativelaminant applications.

What is claimed:
 1. A method of improving water repellency anddurability in fiber, nonwoven, textile, and paper compositionscomprising: a) providing a polymer composition comprising as polymerizedunits: i) from 9.5 to 100 parts by weight of at least one C₁₂ to C₄₀alkyl ester of (meth)acrylic acid; from 0 to 90 parts by weight of atleast one less than C₁₅ ethylenically unsaturated monomer; from 0 to 90parts by weight of at least one ethylenically unsaturated acidcontaining monomer or salts thereof; and from 0 to 10 parts by weight ofat least one cross-linking monomer; and ii) from 0 to 10 parts byweight, based on the polymer weight of at least one cross-linking agent;wherein the polymer composition is an emulsion polymer prepared byemulsion polymerization in the presence of a macromolecular organiccompound with a hydrophobic cavity; b) providing a substrate selectedfrom the group consisting of fiber, nonwoven, textile, and paper; c)coating the substrate with the polymer composition; and d) drying thecoated substrate.
 2. The method of claim 1 wherein the polymercomposition comprises: a) from 40 to 99 parts by weight of at least oneC₁₂ to C₄₀ alkyl ester of (meth)acrylic acid, b) from 0 to 50 parts byweight of at least one monomer selected from the group consisting ofmethyl methacrylate and butyl acrylate; c) from 0 to 50 parts by weightmethacrylic acid; and d) from 0.1 to 5 parts by weight of at least onecross-linking monomer selected from the group consisting of(meth)acrylamide, n-methylol (meth)acrylamide, and mixtures thereof. 3.An article comprising: a substrate selected from the group consisting offiber, nonwoven, textile, and paper coated with a polymer compositioncomprising as polymerized units: i) from 9.5 to 100 parts by weight ofat least one C₁₂ to C₄₀ alkyl ester of (meth)acrylic acid; from 0 to 90parts by weight of at least one less than C₁₅ ethylenically unsaturatedmonomer; from 0 to 90 parts by weight of at least one ethylenicallyunsaturated acid containing monomer or salts thereof; and from 0 to 10parts by weight of at least one cross-linking monomer; and ii) from 0 to10 parts by weight, based on the polymer weight of at least onecross-linking agent; wherein the polymer composition is an emulsionpolymer prepared by emulsion polymerization in the presence of amacromolecular organic compound with a hydrophobic cavity.
 4. An articleaccording to claim 3 wherein the polymer composition comprises: a) from40 to 99 parts by weight of at least one C₁₂ to C₄₀ alkyl ester of(meth)acrylic acid, b) from 0 to 50 parts by weight of at least onemonomer selected from the group consisting of methyl methacrylate andbutyl acrylate; c) from 0 to 50 parts by weight methacrylic acid; and d)from 0.1 to 5 parts by weight of at least one cross-linking monomerselected from the group consisting of methacrylamide, n-methylolmethacrylamide, and mixtures thereof.